Process for absorbing olefines



Patented Jan. 23, 1934 v PROCESS FOR. ABSORB'ING 'OLEFINES Adrianus Johannes van Pski, Amsterdam, -Netherlands, assignor; .byimesne' assignments, to 'Shell'Development Company; San Francisco, 'Calif., acorporation oLDelaware No Drawing. Application June-i 17,4929, Serial No. 371,711,; and in Great". BritainJJulygQ, v19.28 1 Y 8 Claims. (01. 260+98) This invention relatesto a rocession-absorbing a s; st rs; t s w at v mpounds ethylene and/or its hom'ologues bymeansofsuitit is intended t p p ablestrong acids and forlthe manufacture oflthe c d g t 't e" nventionthesaid"drawbacks corresponding esters, 'ethers, alcohols'or other f y 't e lfines"in'acids L compounds. ort mixt-ures or 'acids'in i the 'presence of one or It is anobject of the invention to provide. a ta ya p sfit ature"of process ."ofthe above mentioned nature bywhich which is hereinafter desc bed.

the rate ofabsorption' may be considerably in- "'It-has-been found thatthe-reaction y be creased with respect to the known processes of considerably:"facilitatedwwhen"Performing "t e ,ioi bsorbing olefines. in strong acids. *Another im- "same in p s alyst omprisine portantiobject of'the'invention is to avoidentir'eferricyanic acid o ad alti y- 1y or asfar asis pos'siblethe formation "of unde- 'anic d. a i o a t y sir able oily polymerization products which are rp at y 'a dyanic'acid frequentlyvformed'whenabsorbing olefines in the y be'ilsed. Alsosalts of 'theseacids'or'com- W 5above mentioned manner by the well known p undsderivedfrom'said acidsorfrommobdltometh d *cyanic acid by substituting-one or more atoms Further objects and advantagesof'the invengroups by T ganic tion will appear :as the. description proceeds. It "or'inol'ganic fg l-1p y p y is well, known thatethyl-alcohol, isopropyl alcor in t0 t fi l fl wgohol, butyl alcohol; etc; may beobtainedby "comderived -fr0mthe' above "specified-acids or combining the corresponding olefines'with sulphuric 'p y addition a i o g c acid and hydrolyzingizthe sulphates obtained. compoundsithereto va ta us y us d. .Besides alcohols other compounds'suchas'esters A180 y a h v thanone metallic onethers may be prepared by first absorbing 'ole- "atom in'the'nucleussuch as acidsof-the formula. n25 fines in sulphuric .acid and converting the reac- 8 2 12; H6Fe2(CN) 12 1 11 rwmp unds tion products in a, suitable manner, derived from saidacids'in the manner as specified Theirate of absorption'of olefines by means of above y vSOIIIBiJiIIIBS' advantageously be' used sulphuric acid in the well-known way is generalaccording to the "inV8I1ti0I1. ""S11Ch" acids are ly'slow. By increasing the'stren'gth' "offthe'sulfor edlbycondensation-ofthe complexcyan'ides ..30, phuric acid'the absorption is improved butthe avi g'o e nucleus.

result is that a'larger quantity of undesirable oily The invention also comprisesthe-useof a-r'nixpolymerization products is formed. ture of two" or more 'ofanyof the compounds iiAttemptshave been "made torincrea'se 'the'trate mentioned "ab V e0 fi eS to be absorbed of absorption. 'It has been proposed'to' perform m y be in a P ta tiallrpurestateor the reaction in the presence oi? sm'allquantitiesiof ed w h l0the1ii60ml1011f1d$/iWhebhefiioli110i? 0f isilverisalts or mercury salts which.a'ct'as'catalysts. rt characte t The o efinesto"-.be-treated-.may Y Althoughthe rate of absorption'is'more rapid be obtainedafromaany suitable vso.u rce,-for in- ;when these salts are added, a considerable quanstance from naturalgasor. from gases orproducts 'tity of the above mentioned oily polymerization whiclh are formed.when:distilling/orcracking products isiormed. petroleum or petroleum products. .Also:.the olenttemptsihave also. been'made to improve-the finesmaybe-obtained vfromtheproducts which 1 saidreaction by adding'Iroth-forming substances are .formed ;bytheedestructive hydrogenation :of or emulsifiers and'the like to thesulphuric acid carbonaceous materials -nsuchiascoal; brown-coal, or by dissolving the olefines" in suitable solvents tar,coal.tar, petroleum.;and petroleum products, before bringing them into contact withthesuland other carbonaceous materials which are-suit- ,phuric acid. able iorrtreatmentbyz destructivehydrogenation.

. Although the reaction is in'this way accelerated Thevolefines to-be-treatedmay beseparatediin ."the rate'of absorption'is not asrapidas is desired a more-rorslesspure-state from the above;:men-

'for carryingput the reaction on a commercial tioned...products-but.itiisialsoepossiblento;treat 50 scale. the products such as are: obtained, vfor. instance, Furthermore, notwithstanding the use to! "the by destructive hydrogenation of carbonaceous said.catalysts, .the considerable, quantity of oily materials or by cracking petroleum products productschiefly formed by polymerization Toffthe and which contain certain amounts of olefines, nzolefinesainto hydrocarbons:ofihighenmolecular Without first separating the-- olefines therefrom. eafiinweightr decreasestheultimate.yield-iof the desired If desired the gases obtained, for instance by nitroprusside and acetone) 267, 372 (1892) "cyanicamine (of.

destructive hydrogenation, may be subjected to another operation as, for instance, cracking, to increase the quantity of olefines.

The invention relates to the treatment of all kinds of. olefines including those .with two or more double bonds and also the products obtained by polymerization of olefines of lower molecular Weight. The absorption reaction may.

be performed under elevated pressure and, if desired, also under pressure below atmospheric pressure. In many cases, however, favorable results are obtained by carrying. out the reaction at ordinary pressure. The temperature at which the reaction is carried out may vary within wide limits and may also be below ordinary temperature. If initial materials are employed containing two or more olefines it is possible to eiiect a ready separation of the different olefines by passing them through sulphuric acid of gradually increasing strength, though such separation forms no part of the present invention.

- The catalystsspecified above may be added to- I gether with froth forming, scum forming or emulsion forming substances. In order further to facilitate the absorption, the olefines may be dissolved in suitable solvents, such as gas oil previously treated with sulphuric acid, in order to improve the contact between the acid and the olefines.

The compounds which act as catalysts may be added to the acid in a finely divided state or dissolved or dispersed in suitable liquids.

The concentration of the acid may vary within wide limits depending on the temperaturathe catalyst employed and the nature of the olefines. The reaction may befurther promoted by agitating the acid liquid and/or by introducing the gases through orifices of small diameter into the acid.

As suitable acids for absorbing the oleiinesaccording to this invention sulphuric acid may be used, but also other acids, such as phosphoric acid or suitable sulphonic acids may be employed. It, is not always essential that the quantity of the acid should be equivalent to or more than the quantity of the oleiine or olefines to be absorbed. Sometimes a smaller'quantity of acid will be sufiicient, for instance, if it is intended to a manufacture esters directly. It should be understood that the invention is not in any way limited to the quantity of acid nor to the concentration or the nature of same, provided that invention are as follows:-

.I. Compounds derived, from ferricyanic acid (a) Naz(Fe(CN)5l\ O) or sodium nitroprusside; (b) Acetone sodium nitroprusside (the substance obtained by the reaction between sodium (cf. Bitto. Lieb. Ann.

(0) Nas(Fe(CN)sNO2) or sodium nitrite prusside; (cf. Hofmann,Lieb. Ann. 312, 9 (1900) (d) Na2Fe(CN)5N(OH)SCN or sodiumnitroprusside thiocyanic acid; (of. Chemisch Zentralblatt 1927, I, 1430 (Tarugi)) (e) ,3 ferricyanides for instance 2K(Fe(CN)4),

U)- Na2(Fe(CN)5N1-Ia) or sodium ferripenta- W. Manchot Berichte 45, 287'? /NH2 NA FMONlsNOSO .J

or sodium ferripentacyanic nitrosothiocarbamide (cf. Hofmann, Lieb. Ann. 312, 31 (1900) (h) C6H5CNH3F9 CII) e or benzonitrilferricyanic acid. (of. Baeyer and Villiger Berichte 34, 3617 (1901) Furthermore, different addition compounds from these substances with organic compounds, such as alcohols, ethers, ketones, amines, etc. may be employed.

II. Compounds derived from fer-rocyanic acid 7 (a) Na4Fe(CN)5NO2 or sodium prussonitrite; (of. Lieb. Ann. 312,, 7, 11 (1900)).

(b) NasFMCNhNI-Ia or sodium ferropentacyanicamine; (of. W. Manchot, Berichte 45, 2874 (c) Na3Fe(CN)5CO or sodium ferropentacyanic carbonyl; (of. Manchot, Berichte 45, 2870 (1912)).

(d) Na5Fe(CN)sS039HzO or sodiumprussosulphite; (cf. Lieb. Ann. 312, 4, 5, 26 (1900)).

(e) Na4Fe(CN)sOAsO or sodiumprussoarsenite; (cf. Lieb. Ann. 312, 4 (1900)).

(f) H3(Fe(CN)6)SO3H sulphonic ferrocyanic acid which may be obtained by heating potassium fer'rocyanide with concentrated sulphuric acid at elevated temperature, say 110 centigrade.

Also different addition compoimds obtained from these and the like substances with organic compounds may be used for the purpose of this invention, for instance CeH5CN.I-I4Fe(CN)6 or benzonitrile ferrocyanic acid. Analogous compounds derived from cobalticyanic, acid, cobaltocyanic acid (which itself does not exist but from which different compounds are known, for instance carbonyl cobaltocyanic acid (HaCO (CN) 500) although it should be noted that the same may not alway's have the same constitution as the original one.

Sometimes it is possible to prepare the catalyst in the acid, so that a preceding isolation of the substance is superfluous. This is, for instance, the case when it is intended to use sulphonic Ierrocyanic acid which may be prepared as stated above, in which case the sulphuric acid may at the same time be employed as absorbing acid for the olefines.

The followingexamples serve to illustrate how the invention may be carried into effect:

1. Propylene is passed through'90% sulphuric acid to which 2 per cent of potassium ferricyanide has been added. The propylene is absorbed very rapidly without the formation of .undesired polymerization products. The rate of absorption is considerably higher than ,is"'"the case when known catalysts, for instance, mercury sulphate, are employed.

2. Propylene is passed through sulphuric acid to which a small amount, of sulphonic ferrocyanic acid is added. The total amount of the propylene is absorbed.

3. Ethylene, which is generally absorbed with more'difficulty, is passed at -35 C; through sane-e22 per centssulphuric: acid;-which also *contains .sul-

quantity of sulphonic cferrocyanic. acidis. added,

with the-result:.that 35% of theethylene is 'absorbed.

; 4;.Propylene is passed into 90% sulphuric aci x'in which have been dissolved 5 grams of acetone sodium..nitroprusside: per 100 cc.- of sulphuric :.acid.. .At a rate of 3.7 litres of propyleneper hour per 100 cc. sulphuric acid, the. absorption amounts to 91% without the formation of oily polymerizationproducts.

5. Under the same conditions as in Example 4 but with 5 grams of ferricyanide K2Fe(CN)5, KFe(CN)43H2O and at a rate of 4.1 litres per hour the absorption amounts to 90 per cent.

6. Under the same conditions as in Example 4 but with 5 grams of sodium ferropentacyanic carbonyl and at a rate of 3.7 litres per hour the absorption amounts to 97 per cent.

'7. Propylene is passed through 90% sulphuric acid to which 5 grams of barium platino cyanide per 100 cc. of sulphuric acid have been added; the propylene is easily absorbed without the formation of a substantial amount of polymerization products.

8. Propylene is passed through 90% sulphuric acid to which 5 grams of tetraethylferrocyanide per 100 cc. have been added. The propylene is totally absorbed. After diluting with water and distilling, isopropyl alcohol is obtained with a yield of about per cent.

9. The same experiment as described in Example 8 is carried out, but with diethylnitroprusside, whereby approximately the same results are obtained.

10. At a temperature of 100 C. ethylene is passed through 98% sulphuric acid, to which 5 grams of tetraethyl ferrocyanide have been added. After 38 litres of ethylene have been absorbed per 100 cc. sulphuric acid, no polymerization products were being formed, the mass is diluted with water and ethyl alcohol is obtained by distillation.

l1. 5 grams of hexamethylferrocyanic methylsulphate are added to 100 cc. sulphuric acid. Propylene is passed therethrough and absorbed, only small quantities of oily polymerization products being formed.

12. The same operation as described in Example 11 is carried out but with a catalyst obtained by alkylating potassiumcobalticyanide with diethylsulphate, the result being about the same.

13. Under the same conditions as described in Example 11 ethylene is treated, but with a catalyst consisting of potassiumcarbonylcobaltocyanide, which gives approximately the same result.

14. A gas, obtained by cracking butane and containing 30 per cent of propylene and 11 per cent ethylene is passed through an absorption liquid which is prepared in the following mannerz-To 96% sulphuric acid is added 10 grams per cc. sulphuric acid of potassium ferrocyanide from which the water of crystallization has been removed, Whereafter the mass is heated during one hour at C. Then the concentration of the sulphuric acid is reduced to 90% by adding diluted sulphuric acid whereby the concentration of the potassium ferrocyanide is decreased to approximately 5 grams per 100 cc.

Into this liquid the above mentioned gas is passed whereby the propylene is entirely absorbed even when the rate of passing is very high. Thereafter the gas, which now is freed from propylene P and still contains ethylene is passed through 96 :phonatedferrocyanic 1 acid,- the temperature being maintained now at 100 C. Thereby. the ethylene iswholly absorbed.

.- 15x90 grams :of a butylene are for severalvhours: 80 agitated in an autoclave with 400- grams of 170% .sulphuric acid and Y10 grams of potassium ferrocyanide, whereafter the mass isdiluted with-water .and distilled. A yield of about 80 per cent -of "butyl alcohol is obtained.

'16; At a rate.;.of:'3 litres per=hour; ethylene is passed at a temperature of 100 C. into a solution of 5 grams of dichlor-biphenyl-isonitrile platinum in 100 cc. 96% sulphuric acid. The ethylene is substantially totally absorbed. At M 290 rate of 5 litres per hour the absorption still amounts to approximately 90%.

1'7. 50 grams of on butylene, '70 grams of glacial acetic acid, 10 grams of 96% sulphuric acid and 5 grams of ferrocyanic acid are heated during 8%;95 hours in an autoclave at a temperature of 80 C. Besides a small quantity of butyl alcohol, 70% butyl acetate is obtained.

The aforesaid catalysts may also be advantageously used in the hydration of olefines bytlDO water in the presence of relatively small concentrations of acids and also for the formation of alkyl esters by the direct reaction between olefines and organic acids, for instance acetic acid, as shown in Example 17.

It should be understood that the invention relates to all processes for the manufacture of different substances which involve the step of first absorbing ethylene and/or its homologues in the appropriate strong acids and it should be underi110 stood also that since it is impossible to specify all the substances which may be used, the invention is deemed to include the use, as catalysts for promoting the absorption of ethylene and/or its homologues, of metallic cyano-compounds which 1 15 are chemical equivalents of those referred to above, whatever may be their mode of production.

What I claim is:

1. A process of absorbing unsaturated aliphatic hydrocarbons containing at least one double bond'd20 in the molecule in sulphuric acid, which consists in carrying out the absorption in the presence of complex metallic-cyano compounds.

2. A process of absorbing unsaturated aliphatic hydrocarbons containing at least one double bond 1% in the molecule in sulphuric acid, which consists in carrying out the absorption in the presence of anhydrous complex metallic-cyano compounds.

3. A process of absorbing unsaturated'aliphatic hydrocarbons containing at least one double bond in the molecule in sulphuric acid, which consists in carrying out the absorption in the presence of complex metallic-cyano compounds, and recovering said complexes from the reaction products.

4. A process of absorbing unsaturated aliphaticsim hydrocarbons containing at least one double bond in the molecule in sulphuric acid, which consists in carrying out the absorption in the presence of complex metallic cyano compounds, and recovering the active nucleus of said complexes from the .1 reaction products.

5. A process of absorbing unsaturated aliphatic hydrocarbons containing at least one double bond in the molecule in sulphuric acid, which consists in carrying out the reaction in the presence of 4545 complex metallic-cyano compounds, said compounds being most finely dispersed in a liquid prior to their addition to the absorption acid.

6. A process of the absorption of unsaturated aliphatic hydrocarbons containing at least oneqbo 'double bond in the molecule in sulphuric acid,

-which consists in carrying out the absorption in the presence of complex metallic-cyano compounds, said unsaturated aliphatic hydrocarbons being contained in a gas resulting from treatment of carbonaceous materials.

'7. A process of the absorption of unsaturated aliphatic hydrocarbons containing at least one double bond in the molecule, which consists in dissolving the hydrocarbons in a solvent and carrying out the absorption by'treating the solution in the molecule in sulphuric acid, which consists.

in carrying out the reaction in the presence of complex metallic-cyano' compounds, said compounds being dissolved prior to their addition t the absorption acid. 7

ADRIANUS JOHANNES vAs PESKI. 

